Heterocyclic compounds containing ethylene double bonds and process for their manufacture

ABSTRACT

IN WHICH R1 REPRESENTS A HETEROCYCLIC RING SYSTEM OF AROMATIC CHARACTER WHICH (A) CONTAINS AT LEAST ONE 5-MEMBERED OR 6-MEMBERED HETEROCYCLIC RING WITH AT LEAST ONE RING NITROGEN ATOM, (B) IS FREE OF HYDROGEN ATOMS WHICH (1) ARE BONDED TO RING NITROGEN ATOMS AND (2) WHICH ARE REPLACEABLE BY ALKALI METAL, AND (C) IS BONDED TO A RING MEMBER OF R2 BY MEANS OF A RING MEMBER OR HAS TWO ADJACENT RING MEMBERS IN COMMON WITH TWO ADJACENT RING MEMBERS OF R2, IN WHICH R2 DENOTES A CARBOCYCLIC OR HETEROCYCLIC RING SYSTEM OF AROMATIC CHARACTER WHICH CONTAINS 6 RING MEMBERS, AND WHICH OPTIONALLY IS CONDENSED WITH FURTHER AROMATIC OR HYDROAROMATIC RING SYSTEMS, AND IN WHICH (B) THE METHYL GROUP SHOWN IN THE FORMULA IS IN A P-POSITION TO THE BOND TO R1, IS REACTED WITH A SCHIFF BASE IN THE PRESENCE OF A STRONGLY BASIC ALKALI COMPOUND, WITH THE REACTION MEDIUM TO BE USED BEING A STRONGLY POLAR, NEUTRAL TO BASIC, ORGANIC SOLVENT WHICH (I) IS FREE OF ATOMS, ESPECIALLY HYDROGEN ATOMS, WHICH ARE REPLACEABLE BY ALKALI METAL AND (II) IS PRACTICALLY ANHYDROUS, EXCEPT IN THE CASE OF THE USE OF AN ALKALI HYDROXIDE AS THE STRONGLY BASIC ALKALI COMPOUND IN WHICH CASE THE ALKALI HYDROXIDE MAY HAVE A WATER CONTENT OF UP TO 25%.   R1-R2-CH3   THE PRESENT INVENTION COMPRISES A PROCESS FOR THE MANUFACTURE OF HETEROCYCLIC COMPOUNDS CONTAINING ETHYLENE DOUBLE BONDS. THIS PROCESS IS CHARACTERISED BY REACTING A COMPOUND OF FORMULA

United States Patent 3,732,221 HETEROCYCLIC COMPOUNDS CONTAINING ETHYLENE DOUBLE BONDS AND PROCESS FOR THEIR MANUFACTURE Adolf Emil Siegrist, Basel, Peter Liechti, Binningen, Erwin Maeder, Aesch, Basel-Land, Leonardo Guglielmetti, Birsfelden, and Hans Rudolf Meyer and Kurt Weber, Basel, Switzerland, assignors to Ciba-Geigy A.G., Basel, Switzerland No Drawing. Continuation of abandoned application Ser. No. 588,318, Oct. 21, 1966. This application May 11, 1971, Ser. No. 142,388 Claims priority, application Switzerland, Oct. 28, 1965, 14,902/ 65; July 4, 1966, 9,649/66 Int. Cl. C09b 23/00 US. Cl. 260-240 B 16 Claims ABSTRACT OF THE DISCLOSURE The present invention comprises a process for the manufacture of heterocyclic compounds containing ethylene double bonds. This process is characterised by reacting a compound of formula 1 i git-CH3 in which R represents a heterocyclic ring system of aromatic character which (a) contains at least one S-membered or 6-membered heterocyclic ring with at least one ring nitrogen atom, (b) is free of hydrogen atoms which (1) are bonded to ring nitrogen atoms and (2) which are replaceable by alkali metal, and (c) is bonded to a ring member of R by means of a ring member or has two adjacent ring members in common with two adjacent ring members of R in which R denotes a carbocyclic or heterocyclic ring system of aromatic character which contains 6 ring members, and which optionally is condensed with further aromatic or hydroaromatic ring systems, and in which (b) the methyl group shown in the formula is in a p-position to the bond to R is reacted with a Schitt base in the presence of a strongly basic alkali compound, with the reaction medium to be used being a strongly polar, neutral to basic, organic solvent which 1) is free of atoms, especially hydrogen atoms, which are replaceable by alkali metal and (LII) is practically anhydrous, except in the case of the use of an alkali hydroxide as the strongly basic alkali compound in which case the alkali hydroxide may have a water content of up to 25%.

This application is a streamlined continuation of Ser. No. 588,318, filed Oct. 21, 1966, now abandoned in favor of this streamlined continuation.

Within the framework of the present invention above described in the abstract of the invention 2 main types of reactions according to Formula 1 are above all of importance, and these may be circumscribed as follows:

(1) The reaction of anils of aldehydes of aromatic character, in the manner described under Formula 1, with compounds of formula in which formula (a) G, B and D each denote a ring atom of a S-membered or 6-membered ring system of aromatic character, with at least one of the symbols G, B and D representing a nitrogen atom, and where D may instead of nitrogen also denote a carbon atom and G as well as B may represent carbon, nitrogen, oxygen or sulphur atoms in the arrangement of ring systems which are in themselves known, (b) E represents the ring member supplementation to give a S-membered or 6-membered ring system of aromatic character, containing carbon, nitrogen, oxygen or sulphur atoms in the arrangement of ring systems which are in themselves known, and in which (c) the rings which are formed conjointly with the symbol B may contain further substituents, which like the substituent X do not contain any atoms which may be replaced by alkali, especially hydrogen atoms, and 12 represents the numbers 0 or 1 and q the numbers 0; 1, 2 or 3.

The aforementioned substituents may be of any desired aliphatic, cycloaliphatic, araliphatic or aromatic nature or may represent functional substituents (e.g. carboxylic acid ester groups and the like) as long as they fulfil the preceding condition.

(2) A further important application of the reaction category disclosed under Formula 1 comprises the reaction of anils of aldehydes of aromatic character, in the manner given under the Formula 1, with compounds of formula ,G on, 1

represent a nitrogen atom, and these atoms are present in I the arrangement of ring systems which are in themselves known, (b) E denotes the ring member supplementation to form a S-membered or 6-membered ring system of aromatic character, containing carbon, nitrogen, oxygen or sulphur atoms in the arrangement of ring systems which are in themselves known, and in which (c) the ring formed together with the symbol B may contain further substituents, which like the substituent X do not contain any atoms replaceable by alkali, especially hydrogen atoms, and q may denote the numbers 0, 1, 2 or 3.

These substituents may again, as explained under Formula 1a, be of any desired aliphatic, cycloaliphatic, araliphatic or aromatic nature or may represent functional substituents (e.g. carboxylic acid ester groups).

The reaction which has been discovered in the present process is based in principle on a reaction of the methyl group of compounds of formula category 1) with the azomethine grouping of a SchiiT base (for example benzaniline) with elmination of the amine components, according to the following scheme:

1 IN Ra-CHa A- =CH-R b Alkali M. Here R and R have the significance given above, A-N= represents an amine residue and =CH-R represents an aldehyde residue, in which R denotes a residue of an aldehyde of aromatic character.

The heterocyclic ring system R may consist of one or more rings. At the same time it is a prerequisite in all cases that this ring system R should contain a heterocyclic ring, having 5 to 6 ring members and containing ring nitrogen atoms, this ring in turn being bonded to R and in fact either (a) in such a way that one ring I l I I I atom of this heterocyclic ring is bonded to a ring atom of R by means of one bond, or (b) that this heterocyclic ring has two, in each case adjacent, ring atoms in common with R that is to say that it forms a condensed ring system. The statement that the ring system R may consist of one or more rings, denotes that for example (a) R consists only of one heterocyclic ring having 5 to '6 ring members and containing ring nitrogen atoms, or (b) a heterocyclic compound as defined under (a) contains further carbocyclic rings (especially 6-rings) condensed to it (preferably a benzene or naphthalene ring), or (c) a heterocyclic compound as defined under (a) contains further aromatic rings of carbocyclic or heterocyclic nature bonded via a single valence (that is to say not condensed), or (d) a heterocyclic compound as defined under (a) is condensed with further heterocyclic rings, in which case hetero-atoms may also be common to two rings, or (e) combinations of the abovementioned variants with one another.

One of the reagents to be used for the process of the invention, namely the compound according to Formula 1, is capable of very broad variation within the framework of the definition given above.

The text which follows summarises the basic types and some selected classes of compounds according to Formula 1, without thereby imposing a limitation to these formulae.

(A) Compounds of formula in which R denotes a heterocyclic ring system which contains a S-membered to 6-mernbered heterocyclic ring with two adjacent ring members which are directly bonded to R and at least one nitrogen atom which is exclusively bonded into the ring, and R denotes a benzene ring condensed with the hetero-ring, with the two carbon atoms which belong to both rings and with the carbon atom bonded to the H C-group being in the 1,2,4- position relative to one another. In this case the benzene residue R is with advantage monocyclic and the heterocyclic ring of the residue R is only condensed with R The latter may however of course still contain monovalent substituents, e.g. hydrocarbon residues, which may, like benzene residues or diphenyl residues, also be cyclic. Here emphasis should be placed on the compounds of formula CH3 IL -ll and especially on the benzoxazoles of formula in which R denotes a heterocyclic ring system which contains at least one S-membered to 6-membered heterocyclic ring with a ring member which is directly bonded to R and a nitrogen atom which is exclusively bonded into the ring, and R represents a benzene residue or naphthalene residue bonded to R and to the H c-group in the 1,4-position. Here the ring system R preferably consists of a S-membered to 6-membered heterocyclic ring and a benzene or naphthalene ring condensed with this ring, with the rings referred to again being able to have further substituents, as may be the case for compounds of formula in which R" denotes a benzene residue or naphthalene residue condensed with R in the manner indicated by the valency lines, R denotes a S-membered to 6-membered heterocyclic ring with a ring member directly bonded to the methylphenyl residue and with at least one nitrogen atom exclusively bonded into the ring, and X denotes a hydrogen atom, a chlorine atom, a methoxy group or a methyl group. Possible compounds are especially triazole, oxazole and diazine compounds, for example compounds of formulae in which R" denotes a benzene or naphthalene ring, condensed with the triazole, oxazole or diazine ring in the manner indicated by the valency lines, and Y denotes a hydrogen atom or a benzene residue.

(C) Compounds of formula in which R" denotes a heterocyclic ring system having at most two rings, which contains a S-membered to 6- membered heterocyclic ring with two to three ring members singly and directly bonded to the methylbenzene residue and at least one nitrogen atom exclusively bonded into the ring, X represents a hydrogen atom, a halogen atom, a methoxy group or a methyl group, and n is equal to 2 or 3. R may for example be an oxdiazole, thiadiazole, quinazoline, pyrimidine or 1,3,5-triazine residue. As examples there may here be emphasised the oxdiazole and thiadiazole compounds of formula in which Y denotes an oxygen or sulphur atom.

(D) Compounds of formula in which R'" denotes, for example, a monocyclic benzene residue and X a hydrogen atom, a chlorine atom, a methoxy group or a methyl group, especially triazines of formula Q? RD- N l X: 0

listed below:

N CH, \N/

(20) j 6/ -CHs @3 rr \N N (22) /o o\ H3o-o\N/ N/QOE MQ NN (34) 1. F W3 (35) Z1N @l CoHr N/ CH (37) H, CH3

Qt NN (38) 11-} /N H H3C TQ CHa NN -CHa Ha N

Additionally, the following explanations apply to the preceding formulae:

p- C oHs-CHB (1) Terminal phenyl residues may additionally contain further substituents of the alkyl series (especially having 1 to 4 carbon atoms), the halogen series (especially chlorine) or the alkoxy series (especially those having 1 to 4 carbon atoms). (2) Phenyl residues on striazine rings may additionally contain methyl groups. (3) Amongst substitution products of compounds according to Formula 19 there are also to be included the corresponding 6-phenyl-benzoxazoles as well as the analogous l-naphthoxazoles and 2-naphthoxazoles. (4) The denotes that either a hydrogen atom or a methyl group, but in the entire molecule at least one methyl group, should -be present. (5) The significance (as in the corresponding examples) of the symbols Y and Z is Y =O- or --S- and Z =N or =CH. (6) The symbol CsHs denotes that in this position there may be either a hydrogen atom or a phenyl group.

As may be seen from the preceding compilation, all p-methylphenyl derivatives of nitrogen-containing heterocyclics of aromatic character are in principle accessible to the reaction of the invention and, summarising, the most important categories should again be pointed out, namely such derivatives of pyrrole, pyrazoles, triazoles (1,2,3-, 1,2,4- or 1,3,4), tetrazole, pyridine, pyrimidine, pyrazine, quinazoline, quinoxaline quinolines triazines (1,3,5-, 1,2,4-, 1,2,3-), oxdiazoles (1,2,4-, 1,3,4-), benzoxazoles and naphthoxazoles (iso)oxazoles imidazoles as well as the corresponding ring systems which are condensed with benzene or naphthalene rings where these have not already been named.

The Schilf base to be used as the second reagent in the present process must, as Will be obvious, be free of reactive methyl groups, for example those in the p-position to the azomethane grouping. Possble Schiif bases are, in turn, the (known) condensation products of aldehydes of aromatic character with primary amines (of aliphatic, aromatic or heterocyclic nature), whose amino group is bonded to a tertiary carbon atom. Compounds of this type may accordingly be written as azomethine compounds of Formula. 45 ArCH=NC (tertiary) in which Ar denotes an aromatic residue. In this, either one or both of the components required for the synthesis of the Schitf bases (aldehdye and amine) may contain further substituents, provided the above restriction is observed. Since the amine, especially aniline, residue is split otf during the reaction and is no longer present in the final product, the presence of substituents in this is generally not indicated and is uninteresting. Nevertheless substituents which do not interfere with, or hinder, the reaction, for example chlorine atoms, may be present in this ring also. The benzene residue bonded to the =HC-group may for example carry halogen atoms such as bromine or chlorine or alkoxy groups such as methoxy or ethoxy. Preferred interest attaches to Schifi bases of aromatic aldehydes with anilines, that is to say aromatic aldehyde-anils. Such anils for example correspond to the formula (44) II It in which k and I may be identical or different and denote hydrogen atoms, chlorine atoms or methoxy groups and in which h represents chlorine or, preferably, hydrogen. Adjacent k and I may together also form a lgroup. Another important variant of aromatic anils corresponds to the formula (45a) 11 in which h (as above) represents a hydrogen atom or chlorine and Ar denotes a naphthyl or diphenyl residue. As monoaldehyde suitable for the synthesis of these Schiff bases there may be quoted for example: aldehydes of the benzene series such as benzaldehyde or its halogenated analogues, such as the monochloro-analogues and dichloro-analogues, alkoxybenzaldehydes such as p-methoxy-benzaldehyde, alkylated benzaldehydes, provided these do not contain any pmethyl groups, such as toluyl-aldehyde, xylyl-aldehyde and cumoyl-aldehyde, methylenedioxy-benzaldehyde (piperonal) 4-dimethylamino-benzaldehyde, 4-diethylamino-benzaldehyde, and diphenyl-aldehyde; aldehydes of the naphthalene series such as aand fi-naphthaldehyde, and heterocyclic aldehydes such as for example furfurol and thiophenaldehyde.

As suitable amines there may be named, by way of example, the anilines, naphthylamines or, as an aliphatic representative, tert. butylamine.

Compounds of Formula 1 are reacted with the aldehydeanils in the presence of a strongly polar, neutral to alkaline, organic solvent which is free of atoms, especially hydrogen atoms, which are replaceable by alkali metals. Such solvents are especially represented by di-alkylated acylamides, preferably those of the type in which Alkyl denotes a lower alkyl group (containing 1 to 4 carbon atoms), especially a methyl group, Acyl the residue of a low carboxylic acid (containing 1 to 4 carbon atoms), especially formic acid or acetic acid, or of phosphoric acid, and w gives the basicity of the acid. As important examples of such solvents there may be quoted dimethylforrnamide, diethylformamide, dimethylacetarmide and hexamethyl-phosphoric acid-triamide. It is also possible to use solvent mixtures.

The reaction furthermore requires a strongly basic alkali compound. By the term strongly basic alkali compounds there are to be understood, within the framework of the present invention, such compounds of the alkali metals (1) main group of the periodic table' of elements including ammonium as have a basic strength of at least about that of lithium hydroxide. Accordingly, they may be compounds of lithium, sodium, potassium, rubidium, caesium or ammonium of, for example, the alcoholate, hydroxide, amide, hydride, sulphide or strongly basic ion exchanger types. Potassium compounds of composition in which m denotes an interger of 1 to 6, such as for example potassium hydroxide or potassium tertiary-butylate, are advantageously used (above all when mild reaction conditions as regards reaction temperature appear to be indicated). In the case of alkali alcoholates and alkali (and hydrides) it is here necessary to work in a practically anhydrous medium, whereas in the case of alkali hydroxides water contents of up to 25% (for example contents of water of crystallisation) are admissible. In the case of potassium hydroxide a water content of up to about has proved appropriate. As examples of other alkali compounds which may be used there may be quoted sodium methylate, sodium hydroxide, sodium amide, lithium amide, lithium hydroxide, rubidium hydroxide, caesium hydroxide and the like. Of course it is also possible to work with mixtures of such bases.

In accordance with the preceding explanations an embodiment of the present invention which is important in practice consists of reacting anils of aldehydes of the benzene and naphthalene series with compounds which correspond to the formula in which formula (a) G, B and D each denote a ring atom of a S-membered or 6-membered ring system of aromatic character, with at least one of the symbols G, B and D representing a nitrogen atom, where D may, instead of nitrogen, also denote the carbon atom and G as well as B may represent carbon, nitrogen, oxygen or sulphur atoms in the arrangement of ring systems which are in themselves known, (b) E represents the ring member supplementation for a S-membered or 6-membered ring system of aromatic character containing carbon, nitrogen, oxygen or sulphur atoms in the arrangement of ring systems which are in themselves known, and in which (c) the ring formed together with the symbol B may contain further substituents which do not contain any atoms, particularly hydrogen atoms, which are replaceable by alkali, this reaction being carried out in the presence of an alkali compound having a basic strength of at least that of lithium hydroxide, preferably potassium tertiary-butylate or potassium hydroxide, in a solvent which corresponds to the formula in which Alkyl denotes a low alkyl group, Acyl the residue of a low aliphatic, carboxylic acid or of phosphoric acid and w the basicity of the acid, preferably in dimethylformamide.

It is appropriate to react the compound of Formula 1 with the aldehyde-anils in equivalent amounts, so that no component is present in significant excess. As regards the alkali compound, it is advantageous to use at least the equivalent amount, that is to say at least 1 mole, of a compound having, for example, a KO group, per mole of aldehyde-anil. When using potassium hydroxide a 4- fold to 8fold amount is preferably employed.

The reaction of the invention may generally be carried out at temperatures in the range of between about 10 and C. If alcoholates are used as the potassium compound in the reaction, then the application of heat is generally not necessary. The procedure, is, for example, that the aldehyde-aniline is added to the mixture of the compound of Formula 1, the solvent and the potassium alcoholate, preferably with stirring and with exclusion of air, at a temperature of between 15 and 30 C., whereupon the reaction takes place of its own accord, with a slight temperature rise. When using potassium hydroxide it is frequently necessary to work at higher temperatures. For example the reaction mixture is slowly warmed to 30100 C. and then kept at this temperature for some time, for example /2 to 2 hours. The products may be worked up from the reaction mixture by usual methods which are in themselves known.

The compounds obtainable by the present process are in part known compounds. New compounds are, amongst others, with compounds of the following composition:

rgmworbonaa W in which a represents hydrogen, halogen, the methyl group or the methoxy group, Z and/or Z denotes a ring member =CH or =N- and or represents a hydrogen atom, a phenyl residue or a residue of the series in which (I) at least one residue on differs from hydrogen or phenyl and has the significance of one of the other residues quoted for a, and in which (II) terminal phenyl or naphthyl residues may additionally contain 1 to 3 alkyl groups, 1 to 2 halogen atoms or an alkoxy group.

(III) Compounds of formula in which R' denotes an organic residue bonded to the triazine ring by means of a benzene ring, R a benzene residue bonded in the 1,4-position to the triazine ring and the CH= group, and R an aromatic residue.

(IV) Triazine derivatives of formula in which B represents a phenyl or diphenyl residue, and B represents hydrogen, a phenyl residue or an alkyl group having 1 to 4 carbon atoms, and in which terminal phenyl residues may contain an alkyl group with 1 to 4 carbon atoms, halogen or a methoxy group.

(V) Pyridine derivatives of formula in which V V or V represents hydrogen, a styryl residue or a p-phenylstyryl residue, but in which at least one residue V differs from hydrogen.

(VI) Pyrimidine derivatives of formula in which W denotes a phenyl, diphenyl, l-naphthyl or 2- naphthyl residue.

(VII) Compounds of formula o (52) B1-CH=CH C- l a A1 N C An G in which X represents hydrogen or a methyl group, A denotes a phenyl group, a diphenyl group or a l-naphthyl or Z-naphthyl group, and A represents hydrogen, halogen, an alkyl group containing 1 to 4 carbon atoms, a styryl group or p-phenylstyryl group, and where terminal phenyl or naphthyl groups may additionally contain 1 to 3 alkyl groups, 1 to 2 halogen atoms or an alkoxy group.

(IX) Compounds of formula 3) b in which b represents a hydrogen atom or a methyl group, 7 represents a p-isopropylphenyl, diphenyl, l-naphthyl or Z-naphthyl residue, and 6 denotes a residue of the series 13 where (I) a represents hydrogen or phenyl, e and f represent phenyl, stilbenyl, p-phenylstilbenyl or benzostilbenyl, and furthermore Y represents a bridge member -O, -NH-- or -N(alkyl)-, Where (II) U denotes hydrogen, a styryl residue or a p-phenylstyryl residue, and Where (III) terminal phenyl or naphthyl residues may contain 1 to 3 alkyl groups, 1 to 2 halogen atoms or an alkoxy group.

(X) Compound of general formula in which the symbol Q represents a benztriazole, naphthotriazole, Z-benzoxazole, Z-naphthoxazole, benzidiazine, Z-oxazole, s-triazine, as-triazine, oxdiazole (optionally aryl-substituted) or benzthiazole residue and X and X denote branched alkyl groups, or one of the substituents X and X denotes a phenyl group of two adjacent substituents X and X denote a condensedon carbocyclic ring.

(XI) Compounds of formula in which R" denotes a benzene or naphthalene ring condensed with the triazole ring in the manner indicated by the valency lines, R denotes a benzene residue bonded to the triazole ring and the CH= group in the 1,4

position and R denotes a p-isopropylphenyl, biphenylyl or naphthyl residue.

(XII) Oxazole compounds of formula Ga N/ a in which G denotes hydrogen, an alkyl group having 1 to 4 carbon atoms, a phenyl group, a phenylalkyl group with 1 to 4 carbon atoms in the alkyl group, halogen or a sulphonamide group, G represents hydrogen or an alkyl group or may, together with an adjacent residue G and the benzene ring to which these G-residues are attached, form a naphthalene ring g represents hydrogen or methyl and 1;, denotes a p-iso-propylphenyl, diphenyl, l-naphthyl or Z-naphthyl residue, where terminal phenyl or naphthyl residues may additionally contain 1 to 3 alkyl groups, 1 to 2 halogen atoms or an alkoxy group.

(XIII) Compounds of formula 14 (XIV) Compounds of formula (as) N \\G-R2CH=GH-R R7! N W i Y in which one to two residues 6 represent a styryl or pphenylstyryl residue and the remaining e residues denote hydrogen atoms.

(XVI) Compounds of formula in which T represents hydrogen or a phenyl residue and R represents hydrogen, a styryl residue or a p-phenylstyryl residue.

(XVII) 1,2,4-triazine compounds of formula N Q N/ in which represents a styryl or p-phenylstyryl residue.

(XVIII) Benzthiazole compounds of formula C CH=CH K,

in which M represents a 1,2,4-oxdiazole, 1,3,4-triazole, thiadiazole, s'triazine or bisbenzoxazole residue of formula in which K represents a diphenyl residue or a l-naphthyl or 2-naphthyl residue.

(XIX) Compounds of formula La'CH=CH in which L denotes a diphenyl or naphthyl residue and L hydrogen, a styryl residue or a p-phenylstyryl residue.

(XX) Compounds of formula in which P represents hydrogen, an alkyl group containing 1 to 6 carbon atoms or a phenyl group and P represents hydrogen or a phenyl group.

(XXII) Compounds of formula n which U U and U denote a hydrogen atom, a styryl residue or a phenylstyryl residue and at least one symbol U differs from hydrogen.

(XXIII) Compounds of formula in which W and W denote a hydrogen atom, a styryl group or a p-phenylstyryl group, but at least one symbol W differs from hydrogen.

(XXIV) Compounds of formula UOIhGHQ-W TQCHwHU whose terminal aromatic rings may additionally contain alkyl groups, halogen atoms or alkoxy groups.

In these formulae quoted numbers I to XXIV possible alkyl groups in principle also include long chain alkyl groups, but in practice it is mostly alkyl groups containing up to about 8 carbon atoms, preferably 1 to 4 carbon atoms, and especially branched-chain alkyl groups, which require consideration.

Though again in the case of alkoxy groups higher members, that is to say those containing 4 or more carbon atoms, as well as polyalkyleneoxy groups, are possible, the predominant practical significance resides in alkoxy groups containing 1 to 4 carbon atoms. Amongst the halogens quoted, chlorine is of especial interest.

The new compounds of the formulae of the preceding groups I to XXIV may be used as intermediates, for example for the manufacture of dyestuffs or pharmaceuticals. It is also possible subsequently to introduce acid groups conferring water solubility into the new compounds, by methods which are in themselves known.

A large number of compounds of general Formula 49, especially those of Formulae 50, 51, 52, 53, 54, 55, 56, 57, 61, 111, 158, 306, 363 and 371 may, as has further been found, be used as optical brighteners provided they do not contain any chromophoric groups.

From the point of view of use as optical brighteners for the most varied organic materials in which optical brighteners are desirable, the types of compound which are advantageously accessible by the above process may also be classified as follows:

(a) Compounds of formula in which A denotes a phenyl, diphenylyl or naphthyl residue, A; denotes a phenyl, diphenylyl, naphthyl or stilbenyl residue, and X represents hydrogen, alkyl or halogen.

'(b) Compounds of formula in which A represents hydrogen, an alkyl group having 1 to 18 carbon atoms, an aryl residue, especially a phenyl residue, an aralkyl residue (especially a phenyl-C -alkyl residue) or a halogen atom and s denotes an integer from -1 to 3, preferably 1, and X represents hydrogen, alkyl or halogen.

(c) Compounds of formula in which A represents hydrogen, an alkyl group having 1 to 18 carbon atoms, an aryl residue, especially a phenyl residue, an aralkyl residue especially a phenyl-C -alkyl residue or a halogen atom and s denotes an integer from 1 to 3, preferably 1, and X represents hydrogen, alkyl or halogen.

(d) Compounds of formula in which A, represents the remainder of the benzene or naphthalene ring, A denotes a diphenylyl or naphthyl residue, X represents hydrogen, alkyl or halogen and r represents 1 or 2.

(e) Compounds of formula 7? |'Al N\ N in which A denotes a residue of the series A; denotes a phenyl, diphenylyl or naphthyl residue or a residue A and these quoted aromatic residues may additionally contain 1 to 2 substituents X having the significance of hydrogen, alkyl or halogen, preferably in the phenylene nuclei described under A The categories of compounds emphasised above as regards their brightener effect possess a more or less pronounced fluorescence in the dissolved or finely divided state. They are suitable for optical brightening of the most diverse organic materials of natural or synthetic origin, or of materials containing such organic substances for which optical brightening is relevant. As such materials there may for example be quoted the following group of organic materials, without the recital which follows in any way being intended to express any limitation in this respect:

(I) Synthetic organic high molecular materials such as (A) polymerisation products based on organic compounds containing at least one polymerisable carbon-carbon double bond (homopolymers or copolymers as well as their post-treatment products such as cross-linking products, graft products or degradation products, polymer dilutions and the like), as examples of which there may be quoted: polymers based on cap-unsaturated carboxylic acids (for example acrylic compounds), olefine hydrocarbons, vinyl and vinylidene compounds, halogenated hydrocarbons, unsaturated aldehydes and ketones, allyl compounds and the like; furthermore polymerisation products such as are obtainable by ring opening (for example polyamides of the polycaprolactam type), furthermore formaldehyde polymers, or polymers which are obtainable both by polyaddition and by polycondensation such as polythioethers, polyacetals and thioplastics. (B) Polycondensation products or pre-condensates based on bifunctional or polyfunctional compounds with groups capable of condensation, their homocondensation and cocondensation products as well as post-treatment products (for example saturated and unsaturated, unbranched or branched, polyesters), polyamides, maleate resins, their pre-condensates and products of analogous structure, polycarbonates, silicone resins and others; (C) polyaddition products such as polyurethanes (cross-linked and uncrosslinked) or epoxide resins.

(II) Semi-synthetic organic materials such as for example cellulose esters, nitrocellulose, cellulose ethers, regenerated cellulose or their post-treatment products, and casein plastics.

(III) Natural organic materials with animal or vegetable origin, for example based on cellulose or on proteins such as Wool, cotton, silk, leather, wood compositions in a finely divided form, natural resins, and furthermore rubber, guttapercha, balata as well as their posttreatment products and modification products.

The organic materials requiring consideration may be present in the most diverse processing states (raw ma terials, semi-finished goods or finished goods) and states of aggregation. They may thus be present in the form of the most diverse shaped articles, for example as sheets, profiles, injection mouldings, chips, granules, and foams; films, foils, lacquers, strips, coverings, impregnations and coatings or filaments, fibres, flocks, bristles and wires. The materials quoted may on the other hand also be present in an unshaped state in the most diverse homogeneous and inhomogeneous forms of distribution and states of aggregation, for example as powders, solutions, emulsions, dispersions, sols, gels, putties, pastes, waxes, adhesives and trowelling compositions and the like.

Fibre materials may for example be present as continuous filaments, staple fibres, flocks, hanks, yarns, threads,

fibre fleeces, felts, waddings, flocked structures, woven textile fabrics or laminates, knitted fabrics as well as papers, cardboards or paper compositions and the like.

When used as brighteners, these compounds may be added to the materials quoted either before or during shaping. Thus for example they may be added to the moulding composition in the manufacture of films or other moulded articles, or they may be dissolved, dispersed or otherwise finely divided in the spinning composition before spinning. The optical brighteners may also be added to the starting substances, reaction mixtures or intermediate products for the manufacture of fully synthetic or semisynthetic organic materials, that is to say also before or during the chemical reaction, for example in the case of a polycondensation, a polymerisation or a polyaddition.

The new optical brighteners may of course also be employed in all cases where organic materials of the type in dicated above are combined with inorganic materials in any form. They are distinguished by exceptionally good heat stability, light fastness and resistance to migration.

The amount of the new optical brighteners to be used, relative to the material to be optically brightened, may vary within wide limits. A clear and durable effect can already be achieved with very small amounts, in some cases for example with amounts of 0.001 percent by weight. However amounts of up to about 0.5 percent by weight and more may also be used. For most practical purposes amounts of between 0.01 and 0.2. percent by weight are preferably of interest.

The compounds serving as brighteners may for example also be employed as follows: (a) mixed with dyestuffs or pigments or as an additive to dye baths, printing, etching or reserve pastes. Further also for the post-treatment of dyeings, prints or discharge prints; (b) mixed with so-called carriers, antioxidants, light protection agents, heat stabilisers, chemical bleaching agents or as an additive to bleaching baths; (c) mixed with cross-1ink ing agents, finishing materials such as starch or synthetically produced finishes; (d) in combination with detergents, where the detergent and the brightener may be separately added to the wash baths to be used, or preferably detergents are used which contain the brightener mixed into them; (e) in combination with polymeric carriers (polymerisation, polycondensation or polyaddition products), in which the brighteners are optionally introduced alongside other substances in a dissolved or dispersed form, (f) as additives to the most diverse industrial products in order to make these more marketable or to avoid disadvantages in their usability, for example as an additive to glues, adhesives, paints and the like.

The compounds which have been emphasised as optical brighteners may also be used as scintillators for various photographic purposes, such as for electrophotographic reproduction or for super-sensitisation.

In the tabes which follow later on, symbols have the following significance:

Column I=formula number Column II=stn1ctural elements Column III=crude yield in percent Column IV=recrystallisation medium, with these being designated by the numbers listed below: 1=water, 2=ethanol, 3=dioxane, 4=dimethylformamide, 5=tetrachlorethylene, 6=chlorobenzene, 7=o-dichlorobenzene, 8=trichlorobenzene, 9=toluene, 10=n-hexane, 1l=xylene.

Column V=colour of the purified reaction of product, with the latter having been designated by the numbers listed below: 1=colourless, 2=alrnost colourless, 3=pale green, 4=light green, 5=pale yellow, 6=light yellow, 7=yellow, 8=pa1e greenish yellow, 9=light greenish yellow, 10=greenish yellow.

Colunm VI=melting point (uncorrected) in C.

Column V1I=elementary formula and analytical data (upper line calculated, lower line found).

19 EXAMPLE 1 8.63 g. of the compound of formula and 7.05 g. of 4'-methoxybenzal-aniline (C H N=HCC H OCH are stirred into 200 ml. of anhydrous dimethylformamide with exclusion of air, and are all at once treated with 11.2 g. of potassium tertiary-butylate. The colour of the reaction mixture changes immediately from pale yellow to dark blue and the temperature rises in the course of 10 minutes by about 12 C. The mixture is stirred for a further 15 minutes without external warming, during which the temperature drops by about 3 C. Thereafter 400 ml. of water are added dropwise at 5 to 15 C. and the reaction product is filtered off and washed with water until neutral.

The moist filter residue is now dissolved in 270 ml. of dimethylformamide with warming, treated with 25 ml. of 10% hydrochloric acid and after a few minutes with 300 ml. of water and cooled to about 10 C. After filtration, washing wth water and methanol and subsequent drying about 11.7 g., corresponding to 93% of theory, of the compound of formula are obtained in the form of a pale yellow powder of melting point 206 to 207.5 C. Recrystallising this three times from tetrachlorethylene with the aid of fullers earth yields pale yellow glistening platelets of melting point 214 to 214.5" C.

Analysis.--C H ON (377.43). Calculated (percent): C, 79.55; H, 5.07; N, 11.13. Found (percent): C, 79.80; H, 5.11; N, 11.24.

If instead of the 7.05 g. of 4-methoxybenzalaniline 6.05 g. of benzalaniline are used, then 10.4 g., corresponding to 90% of theory, of the compound of formula are obtained in the form of a beige-yellow light-coloured powder which melts at 171 to 171.5 C. After three recrystallisations from tetrachlorethylene with the aid of fullers earth pale greenish yellow glistening platelets of melting point 173.5 to 174 C. are obtained.

Analysis.C H N (347.40). Calculated (percent): C, 82.97; H, 4.93; N, 12.10. Found (percent): C, 82.96; H, 5.04; N, 12.23.

20 EXAMPLE 2 7.1 g. of 1-[6-phenyl-benzoxazolyl-(2')]-4-methylbenzene of formula and 4.53 g. of benzalaniline are stirred into 150 ml. of anhydrous dimethylformamide with exclusion of air and treated all at once with 7.45 g. of potassium tertiarybutylate. The colour of the reaction solution changes immediately from yellow to reddish brown and the temperature rises over the course of 4 minutes, for example from 20 C. to 31 C. The mixture is stirred for a further 10 minutes without external warming, during which the temperature falls by about 5 C. Thereafter 350 ml. of Water are added dropwise at 5 to 15 C. and the precipitated reaction product is filtered off and Washed with water until neutral.

The moist filter residue is now dissolved in 250 ml. of dimethylformamide with warming, treated with 25 ml. of 10% hydrochloric acid and after a few minutes with 350 ml. of Water and cooled to about 10 C. After filtering, washing with Water and methanol and subsequent drying about 5.38 g., corresponding to 57.7% of theory, of 4-[6'- phenyl-benzoxazolyl-(Z)]-stilbene of formula are obtained in the form of a pale yellowish beige powder of melting point 222 to 223 C. Three recrystallisations from tetrachlorethylene with the aid of fullers earth yield pale greenish yellow glistening platelets which melt at 226 to 226.5 C.

Analysis.C -;H ON (373.43). Calculated (percent): C, 86.84; H, 5.13; N, 3.75. Found (percent): C, 86.71; H, 5.03; N, 3.75.

If instead of the 4.53 g. of benzalaniline 5.3 g. of 4'- methoxybenzalaniline are used then 6.2 g., corresponding to 61.6% of theory, of the compound of formula 0 oou=onoorn formula and 4.53 g. of benzalaniline may be used to produce 8.1 g., corresponding to 66.2% of theory, of the compound of formula After three recrystallisations from ethanol with the aid of activated charcoal colourless glistening platelets of activated charcoal colourless glistening platelets of melting point 194 to l94.5 C. are obtained.

Analysis.C H O N S (488.65). Calculated (percent): C, 71.28; H, 6.60; N, 5.73. Found (percent): C, 71.01; H, 6.65; N, 5.73.

EXAMPLE 3 7.13 g. of Z-diphenylyl-(4)-6-1nethylbenzoxazole of formula and 4.53 g. of benzalaniline are stirred into 200 ml. of anhydrous dimethylformamide with exclusion of air and treated all at once with 7.45 g. of potassium tertiary butylate. The colour of the reaction solution changes immediately from pale yellow to dark brown and the temperature rises by 5 to C. over the course of 4 minutes. The mixture is stirred for a further 35 minutes without external warming, during which the temperature falls by a few C. Thereafter 350 ml. of water are added dropwise at 5 to C. and the precipitated reaction product is filtered 0E and washed with water until neutral.

The moist filter residue is now dissolved in 200 ml. of dimethylformamide with warming, treated with 25 ml. of 10% hydrochloric acid and after one hour with 200' ml. of water, and cooled to about 10 C. After filtering, washing with water and methanol and subsequent drying about 6.3 g., corresponding to 67.5% of theory, of the compound of formula (110) /O 0 11:0 Hfi Q listed in the table which follows may be prepared in a similar manner, with the duration of the reaction being extended to minutes.

I As X0 A9 III IV V VI VII 112 H H 77. 5 2 1 146-145. 5 0 H150 N:

c, 84.82; H, 5.09; N, 4.71 c, 84.87; H, 5.24; N, 4.55

113 H CH3 77. 3 2 1 141-141. 5 (12511230 N:

C, 84.95; H, 6.56; N, 3.96 CH;; 0, 84.76; H, 6.68; N, 4.00

- 0 CH 0, 83.35; H, 5.25; N, 3.47 0, 83.23; H, 5.12; N, 3.45

115 H -C1 51. 4 5 5 199-199. 6 CzzHmOzNCl:

- 0 CH3 0, 73.03; H, 4.46; N, 3.87 0, 73.15; H, 4.51; N, 3.90

116 H H 97 5 3 215-216 CnHwON:

0, 86.84; H, 5.13; N, 3.75 o, 86.85; H, 5.22; N, 3.75

117 -2: H CH3 92. 1 5 2 199. 5-200 C H210 N:

-' C, 86.68; N, 6.34; N, 3.2-6 -CH1 0, 86.72; N, 6.38; N, 3.21

118 H 87. 5 6 9 289-289. 5 C 3:1H23ON:

- c, 88.17; H, 5.16; N, 3.12 C, 87.98; H, 5.19; N, 3.15

119 H CH3 3/2 1 185. 5-186 (12 1 12 0 H:

I 0, 86.32; H, 5.25; N, 3.47 (|1CH3 o, 86 27; H, 5.22; N, 3.53 CH3 c, 87.91; H, 5.00; N. 3.31 C, 87.75; H, 4.86; N, 3.45

121 -CH3 74. 4 3/2 3 179. 5-180. 5C25H210N:

0, 86.79; H, 5.46; N, 3.62 c, 85.59; H, 5.53; N, 3.63

II I As Xe A9 III IV V VI VII 122 -CH; 100 4 9 259-259. 5 034111 N:

C, 88.09; H, 5.44; N, 3.02 C, 87.79; H, 5.48; N, 3.06

123 CH3 78. 6 3/2 9 228-228. CuHnO N:

C, 87.84; H, 5.30; N, 3.20 C, 87.50; H, 5.44; N, 3.30

124 -CH3 85. 0 3/2 10 202. 5-203 032E230 N C, 87.84; H, 5.30; N, 3.20 C, 87.59; H, 5.41; N, 3.35

125 -CH3 66. 4 2 5 200-201 023E200 NC Cl C, ;H, 4.78; N, 3.32 c, 79.95; H, 4.61; N, 3.40

126 --CH; 52. 0 10/11 5 191. 5-192 CznHzgOzN:

- 0 CH3 C, 83.43; H, 5.55; N, 3.36 c, 83.35, H, 5.31; N, 3.29

EXAMPLE 4 5.93 g. of 1-[5',6'-dimethyl-benzoxazolyl-(2')]-4-methylbenzene of formula Yield: about 12.8 g., corresponding to 90.5% of theory. Greenish yellow fine needles from o-dichlorobenzene.

Melting point: 296.5 to 298.5 C.

Analysis.-C H ON (565.68). Calculated (percent): C, 89.17; H, 5.52; N, 2.48. Found (percent): C, 88.96; H, 5.70; N, 2.64.

HaC

\ N/CQ-Olia [melting point: 207 to 207.5 C.] and 9.06 g. of benzalaniline are stirred into 250 ml. of anhydrous dimethylformamide with exclusion of air and treated all at once with 16.8 g. of potassium tertiary butylate. The light beige reaction mixture immediately assumes a violet brown colour and the temperature rises by 6 C. The mixture is stirred for a further 90 minutes without external warming and thereafter firstly 300 ml. of water and then 100 ml. of 10% strength aqueous hydrochloric acid are added dropwise. The precipitated reaction product is filtered 01f, washed with water and methanol and dried. About 4.5 g., corresponding to 43.5% of theory, of the compound of formula are obtained in the form of a brown powder. After chromatography in tetrachlorethylene on activated aluminium oxide and recrystallisation from dioxane/ethanol light greenish yellow fine needles of melting point 222 to 223 C. are obtained.

Analysis.--C H ON (413.49). Calculated (percent): C, 87.14; H, 5.61; N, 3.39. Found (percent): C, 87.12; H, 5.62; N, 3.49.

The following benzoxazole derivatives may be prepared in a similar manner.

Yield: 22% of theory. Light greenish yellow fine glistening needles from tetrachloroethylene. Melting point 260 to 260.5 C.

Analysis.C H ON (399.47). Calculated (percent): C, 87.19; H, 5.30; N, 3.51. Found (percent): C, 87.04; H, 5.32; N, 3.71.

EXAMPLE 5 14.8 g. of the compound of formula EQCH;

and 9.6 g. of benzalaniline are stirred into 200 ml. of anhydrous dimethylformamide with exclusion of air and treated all at once with 16.8 g. of potassium tertiary butylate. The colour of the reaction mixture changes immediately from pale yellow to dark green and the temperature rises by about 7 C. in the course of 15 minutes. The mixture is stirred for a further 1% hours without external warming, during which the temperature falls by about 5 C. Thereafter 300 ml. of water are added dropwise at 10 to 20 C. and the reaction product is filtered and washed with water until neutral.

The moist filter residue is now dissolved in 300 ml. of dimethylformamide with warming, treated with 25 ml. of 10% strength hydrochloric acid and after 50 minutes with 300 ml. of water and cooled to about 10 C. After filtering, washing with water and methanol and subsequent drying about 18.1 g., corresponding to 94.1% of theory, of the compound of formula and 10.55 g. of 4'-methoxybenzalaniline are stirred into 200 ml. of anhydrous dimethylformamide with exclusion of air and treated all at once with 11.2 g. of potassium tertiary-butylate. The colour of the reaction mixture changes immediately from pale yellow to blue-green and the temperature rises by only about 12 C. over the course of 4 minutes. The mixture is stirred for a further 2 /2 hours without external warming, during which the temperature again drops. Thereafter 400 ml. of water are added dropwise at 10 to C. and the reaction product is filtered off and washed with water until neutral.

The moist filter residue is now dissolved in 3 l. of dimethylformamide with warming, treated with ml. of 10% strength hydrochloric acid and after 1 hour with 3 l. of Water and cooled to about 10 C. After filtering, washing with water and methanol and subsequent drying about 10.5 g., corresponding to 83.5% of theory, of 2,5- bis-[4" methoxy-stilbenyl-(4')]-1,3,4 thiadiazole of formula If instead of the 9.6 g. of benzalaniline 10.6 g. of 4'- methoxybenzalaniline are used then 18.9 g., corresponding to 94.2% of theory, of the compound of formula are obtained in the form of yellow fine needles which melt at 163.5 to 165 C. On recrystallising three times from tetrachloroethylene with the aid of fullers earth, luminous yellow felted small needles of melting point 167.5 to 168.5 C. are obtained.

l ll

are used then about 10.8 g., corresponding to 89% of theory, of 2,5-bis-[4"-methoxy-stilbenyl-(4)]-1,3,4-oxdiazole of formula Analysis.C H ON (414.48). Calculated (percent): C, 84.03; H, 5.35; N, 6.76. Found (percent): C, 84.14; H, 5.42; N, 6.89.

Using 10.8 g. of 4'-chlorobenzalaniline about 19.8 g., corresponding to 94.5% of theory, of the compound of formula are obtained. Yield: 94.5 of theory. Pale yellow very fine crystals from dimethylformamide/ethanol. Melting point 185 to 186 C.

Analysis.C H N Cl (418.93). Calculated (percent): C, 80.28; H, 4.57; N, 6.69. Found (percent): C, 80.06;

EXAMPLE 6 6.65 g. of the compound of formula are obtained in the form of a light yellow powder which after three recrystallisations from o dichlorobenzene with the aid of fullers earth yields pale yellow glistening platelets of melting .point 311 to 311.5" C.

Analysis.-C H O N (486.54). Calculated (percent): C, 78.99; H, 5.39; N, 5.76. Found (percent): C, 78.90; H, 5.67; N, 5.78.

In a similar manner, 3-[4-methyl-phenyl-(1')]-5-phenyl-1,2,4-oxdiazole of formula and 3,5-di-[4-methyl-phenyl-(l)]-1,2,4-oxdiazole of formula may be used to produce the 1,2,4-oxdiazole derivatives of formula which are listed in the following table.

I T1 T III IV V VI VII 142 H H 70.2 1 2 169459.50 CzzHmONn! c, 81.46; H, 4.97; N, 8.64 c, 81.51; H, 4.91; N, 8.78

1 13 H 75.0 5 1 228228.5 CzsHzoONai C, 83.97; H, 5.03; N, 7.00 c, 84.20; H, 5.15; N, 5.71

144 H 54.5 5 s 245.5-247 CauHnONaZ CH=CH c, 84.48;]1, 5.20; N, 5.51 0, 84.51; H, 5.25; N, 6.63

145 91.7 7 9 329-330 CnHanONat CH=GH- c, 21.17; H, 5.23; N, 4.84 O, 87.14; H, 5.28; N, 4.79

EXAMPLE 7 are obtained in the form of a yellow powder of melting 10.8 g. of 2,4-diphenyl-6-[4'-methylphenyl (1)]-1,3,5- triazine of formula and 7.05 g. of 4'-methoxybenzalaniline are stirred into 200 m1. of anhydrous dimethylformamide with exclusion of air and treated all at once with 11.2 g. of potassium tertiarybutylate. The colour of the reaction mixture changes immediately from light beige to bluish violet and the temperature rises by a few C. over the course of 2 minutes. The mixture is stirred for a further 1 hour without external Warming during which the temperature again drops somewhat. Thereafter 400 ml. of water are added dropwise at 10 to 15 C. and the reaction mixture is filtered and washed with Water until neutral.

The moist filter residue is now dissolved in 120 ml. of dimethylformamide with warming, treated With 25 ml. of 10% strength hydrochloric acid and after a few minutes with 120 ml. of water and cooled to about 10 C. After filtering, washing with water and methanol and subsequent drying about 14.7 g., corresponding to 100% of theory, of 2,4-diphenyl 6 [4-methoxy-sti1benyl-(4')]- 1,3,5-triazine of formula (147) point 243.5 to 246.5 C. After chromatography in tetrachlorethylene on activated aluminium oxide and recrystallisation from dioxane-ethanol, pale greenish yellow felted small needles of melting point 235.5 C. are obtained.

AnaIysis.C H ON (441.51). Calculated (percent): C, 81.61; H, 5.25; N, 9.52. Found (percent): C, 81.70; H, 5.38; N, 9.45.

EXAMPLE 8 11.7 g. of 2,4,6 tri [4-methylphenyl-(1)]-l,3,5-triazine of formula and 18.1 g. of benzalaniline are stirred into 350 ml. of anhydrous dimethylforrnarnide with exclusion of air and treated all at once with 28.0 g. of potassium tertiarybutylate. The colour of the reaction mixture changes immediately from pale yellow to violet and the temperature rises over the course of 5 minutes by about 10 C. The mixture is stirred for a further 1% hours without external warming, during which the temperature again drops. Thereafter 350 ml. of water are added dropwise at 10 to 20 C. and the reaction product is filtered OE and washed with Water until neutral.

The moist filter residue is now dissolved in 500 ml. of dimethylformarnide with warming, treated with 50 ml. of 10% strength hydrochloric acid and thereafter with 500 ml. of water. The mixture is cooled to about 10 C., filtered 0E, and the residue first washed with water, then with methanol and dried. About 20.4 g., corresponding to 99.5% of theory, of 2,4,6-tri-[stilbeny1-(4)]-l,3,5-triazine of formula /N 1'4 it 29 30 are obtained in the form of light yellow very fine small 150 ml. of strength hydrochloric acid and a further needles wh1ch melt at 251 to 254 C. After four recrystal- 250 ml. of water are successively added dropwise at 10 lisations from tetrachlorethylene with the aid of fullers to C. The precipitated reaction product is filtered off, earth light greenish yellow small needles of melting point washed with water until neutral and freed of a by-product 275 to 277 'C. are obtained. 5 by further washing with methanol. After drying about Analysis.-C H N (615-78)- Calc e (perce 19.7 g., corresponding to 96.2% of theory, of 2,4,6-tri- 7 5.40; 6.82- Found (p [stilbenyl-(4)]-1,3,5-tri'azine of Formula 149 are ob- H, 5.50; N, 6.96. tained in the form of a yellow powder which melts at If Instead of ibenlalaniline of 262 to 267 C. After chromatography in tetrachlorethylggilgi gg g g e g'; Eigh 3 2 I -regl g 10 ene on activated aluminium oxide and subsequently three o n- -m x stilbenyl (4 )14,354riazine of formula y recrystalhsanons from tetrachlorethylene, light greenish H 00 CH=CH ('3 (I) CH=OH OCHa N 9 O are obtained in the form of a yellow powder of melting yellow felted small needles of melting point 293 to 293.5 point 263.5 to 265 C. After chromatography in 0-di- C. are obtained.

chlorobenzene on activated aluminium oxide and two re- Analysis.C H N (615.78). Calculated (percent): crystallisations from tetrachlorethylene yellow very fine 35 C, 87.77; H, 5.40; N, 6.82. Found (percent): C, 87.55; small needles of melting point 300 C. are obtained. H, 5.55; N, 6.98.

Analysis.--C H N (487.57). Calculated (percent): If instead of the 18.1 g. of benzalaniline 25.73 g. of cent): C, 81.68; -H, 5.57; N, 5.95. Found (percent): C, diphcnyl-(4)-aldehyde-anil are used and the reaction is 81.53; H, 5.51; N, 5.87. carried out for minutes at C., then the 2,4.6-tri- 40 [4"-phenyl-stilbenyl-(4)]-1,3,5-triazine of formula -@Q N l 0 in lie EXAMPLE 9 is obtained. Yield: 93.1% of theory. Greenish yellow 117 g 0f 2 4 4, methy1pheny1 (1,) 3 crystals from o-dichlorobenzene. Melting point: 361 to 362 C. azine of Formula 148, 18.1 g. of benzalamlme and 12.6 g. of potassium hydroxide powder containing about 10% C dcalculateg g f water are stirred into 300 ml. of dimethylformamide with 2 i 01m (Percen exclusion of air, in the course of which a dark blue colour is produced after a few minutes. The temperature is The following stl lbenyl'1,3,5'tT1aZ1ne derlvaztlve's y raised to C. over the course of 1 hour, and the mixbe P p 111 a slmllaf 013111161? From f fl ture stirred for a further 40 minutes at this temperature ylphenyl-(l')]-l,3,5-tr1az1ne of Formula 148 and 4 -chloand then cooled to about 10 C. Now ml. of water, robenzalaniline, the compound of formula Yield: 94.0% of theory. Light yellow very fine small neeedles from tetrachlorethylene. Melting point: 315 to 317 C.

Analysis.-C H N Cl (719.12). Calculated (percent): C, 75.16; H, 4.21; N, 5.84. Found (percent): C, 75.17; H, 4.22; N, 6.00.

From 2,4-diphenyl-6- [4'-methy1phenyl-( 1) ]-1,3,5-triazine of Formula 146 and diphenyl-(4)-aldehyde-anil, the compound of formula Yield: 98.5% of theory. Light yellow very fine needles from tetrachlorethylene. Melting point: 284 to 285 C.

Analysis.-C H 5N (487.57). Calculated (percent): C, 86.21; H, 5.17; N, 8.62. Found (percent): C, 86.35; H, 5.28; N, 8.54.

From 2,4,6-tri-[2',4'-dimethyl pheny1-(1)]-1,3,5-triazine of formula 20 and diphenyl-(4)-aldehyde-anil, the compound of formula 33 Yield: 100% of theory. Yellow very fine small needles from xylene. Melting point: 162 to 162.5 C.

Analysis.-'C H N (886.16). Calculated (percent): C, 89.46; H, 5.80; N, 4.74. Found (percent): C, 89.16; H, 5.83; N, 4.68.

34 Analysis. C H N (513.61). Calculated (percent): C, 86.52; H, 5.30; N, 8.18. Found (percent): C, 86.46; H, 5.03; N, 7.99.

The 1,3,5-triazine derivatives of formula 158 N EXAMPLE H G a BloII=0 -o o --OH=OHB 16.87 g. of 2,4-d1-[4-methylphenyl (1')]-6-phenyl- {Q 1,3,5-triazine of formula (150 N 10 0 H3O 3- CH8 5 listed in the following table may be produced in a similar manner.

I B; 13. III IV v VI VII 159 CH3 97 0 9/10 6 230.5-231 CnHuNaZ o, 86.4; n, 6.19; N, 7.38

COH0 c, 86.33; ,608; 01,755

160 Q Q 94-3 5 8 240.5- 241 CiaHsiNa:

0, 87.58; H, 5.30; N, 7.13 c, 87.44; H, 5.55; N, 7.13

101 H 04.0 1 0 851-8525 001mm:

.89; H, 5.30; N, 6.31 0, 88.33; H, 5.43; N, 6.28

162 CH3 98.0 3/2 10 325-328 C53H43Na2 I c, 88.18; H, 5.00; N, 5.82 4 343113 0, 88.37; H, 6.28; N, 5.80

- c, 89.04; H, 5.30; N, 5.00 0, 88.08; H, 5.51; N, 5.73

[Melting point: 218 to 218.5 C.], 18.1 g. of benzalaniline EXAMPLE 11 and 50 g. of potassium hydroxide powder containing about 10% water are stirred into 400 ml. of dimethylformamide with exclusion of air, during which a violet colour is produced after a few minutes. The temperature is raised to 60 C. over the course of minutes, and the mixture stirred for a further 30 minutes at this temperature and then cooled to room temperature. Now 50 ml. of water and 500 ml. of 10% strength hydrochloric acid are successively added dropwise. The precipitated reaction product is filtered off, washed with water until neutral and freed of a by-product by further washing with 300 ml. of methanol. After drying about 24.8 g., corresponding to 96.6% of theory, of 2,4-di-[stilbenyl-(4')]-6-phenyl-l,3,5- triazine of formula 14.8 g. of the compound of Formula 131, 9.06 g. of benzalaniline and 25 g. of potassium hydroxide powder containing about 10% water are stirred into 300 ml. of dimethylformamide with exclusion of air, during which a violet colour gradually develops. The temperature is raised to C. over the course of 30 minutes, and the mixture stirred for a further 30 minutes at this temperature and then cooled to room temperature. Now ml. of water and 260 ml. of 10% strength hydrochloride acid are successively added dropwise. The precipitated reaction product is washed with a great deal of water and thereafter with 600 ml. of methanol and is dried. About 16.7 g., corresponding to 87.0% of theory, of the comare obtained as a light yellow powder. After chromatography in tetrachlorethylene on activated aluminium oxide and recrystallisation from tetrachlorethylene practically colourless crystals of melting point 241 to 241.5 C. are obtained.

pound of Formula 132 are obtained in the form of a yellow powder which melts at 159.5 to 160 C. After chromatography in tetrachlorethylene on activated aluminium oxide and recrystallisation from dioxane-ethanol practically colourless felted fine small needles of melting point 164.5 to C. are obtained.

35 Analysis.C H N (384.46). Calculated (percent): C, 87.47; H, 5.24; N, 7.29. Found (percent): C, 87.20; H, 5.10; N, 7.32.

The following quinazoline derivatives may be prepared in a similar manner.

Yield: 94.3% of theory. Light yellow felted fine small needles from tetrachlorethylene. Melting point 226.5 to

Analysis.C H N (460.55). Calculated (percent):

C, 88.66; H, 5.25; N, 6.08. Found (percent): C, 88.46;

Yield: 97.0% of theory. Light greenish yellow glistening small needles from dioxane-ethanol. Melting point: 243 to 243.5 C.

Analysis.C H- N (460.55). Calculated (percent): C, 88.66; H, 5.25; N, 6.08. Found (percent): C, 88.42; H, 5.43; N, 6.15.

Yield: 96.5% of theory. Luminous greenish yellow fine small needles from o-dichlorobenzene. Melting point: 384 to 385 C.

AnaIysis.C H N (638.77). Calculated (percent): C, 90.25; H, 5.37; N, 4.39. Found (percent): C, 90.16; H, 5.41; N, 4.45.

Yield: 87.5% of theory. Light yellow felted small needles from dioxane-ethanol. Melting point: 166 to 166.5 C.

Analysis.-C H N (384.46). Calculated (percent): C, 87.47; H, 5.24; N, 7.29. Found (percent): C, 87.46; H, 5.34; N, 7.21.

Yield: 92.5% of theory. Pale yellow felted small needles from tetrachlorethylene. Melting point: 242 to 242.5 C.

Analysis.C H N (460.55). Calculated (percent): C, 88.66; H, 5.25; N, 6.08. Found (percent): C, 88.71; H, 5.32; N, 5.84.

Yield: 92.0% of theory. Practically colourless very fine crystals from tetrachlorethylene. Melting point: 218 to 219 C.

AnaIysis.--C H N (384.46). Calculated (percent): C, 87.47; H, 5.24; N, 7.29. Found (percent) C, 87.52; H, 5.33; N, 7.54.

Yield: 97.7% of theory. Pale yellow glistening small crystals from o-dichlorobenzene. Melting point: 300 to 301 C.

Analysis.C H N (460.55). Calculated (percent): C, 88.66; H, 5.25; N, 6.08.'Found (percent): C, 88.73; H, 5.31; N, 5.93.

EXAMPLE 12 10.31 g. of 3 [4-methyl-phenyl-(1)]-5,6-diphenyl- 1,2,4-triazine of formula (melting point: 137.5 to 138 C.), 6.04 g. of benzalaniline and 16.7 g. of potassium hydroxide powder containing about 10% of water are stired into 200 m1. of dimethylformamide with exclusion of air, during which a yellowish brown colouration gradually develops. The temperature is raised to 60 C. over the course of 30 minutes, and the mixture stirred for a further 30 minutes at this temperature and then cooled to room temperature. Now 100 ml. of water and 200 ml. of 10% strength hydrochloric acid are successively added dropwise. The precipitated reaction product is Washed with a great deal of water and with 500 ml. of methanol and is dried. About 9.5 g., corresponding to 69.2% of theory, of 3 [stilbenzyl (4')] 5,6-diphenyl-1,2,4-triazine of formula 38 are obtained in the form of a light yellow powder. After three recrystallisations from dimethylformamide-ethanolwater with the aid of activated charcoal, light yellow very fine felted crystals of melting point 202.5 to 203.5 C. are obtained.

Analysis.C H N (411.48). Calculated (percent): C, 84.64; H, 5.14; N, 10.21. Found (percent): C, 84.60: H, 5.32; N, 10.24.

The following 1,2,4-triazine derivative is obtained in a similar manner:

Yield: 85.5% of theory. Light yellow gistening small needles from dimethylformamide. Melting point: 264 to 265 C.

Analysis.C H N (487.57). Calculated (percent): C, 86.21; H, 5.17; N, 8.62. Found (percent): C, 86.04; H, 5.05; N, 8.40.

EXAMPLE 13 12.96 g. of the compound of Formula 101, 9.1 g. of benzalaniline and 25 g. of potassium hydroxide powder containing about 10% of water are stirred into 300 m1. of dimethylformamide with exclusion of air, during which a red colouration gradually develops. The temperature is raised to 60 C. over the course of 30 minutes, and the mixture stirred for a further 30 minutes at this temperature and then cooled to room temperature. ml. of water and 240 ml. of 10% hydrochloric acid are now successively added dropwise. The precipitated reaction product is washed with a great deal of water and thereafter with 80 ml. of methanol, and is dried. About 15.7 g., corresponding to 90.5% of theory, of the naphthtriazole derivative of Formula 103 are obtained in the form of a beige powder which melts at 173.5 to 174 C. Three recrystallisations from tetrachlorethylene with the aid of fullers earth yield pale greenish yellow glistening platelets of melting point 182 to 182.5 C.

Analysis.C H N (347.40). Calculated (percent): C, 82.97; H, 4.93; N, 12.10. Found (percent): C, 83.07; H, 4.94; N, 12.09.

The naphthtriazole derivatives of the formula /N-CH=CH-Bs listed in the following table may be prepared in a similar 1 II B, III IV V VI VII 00H. 0, 70.55; H, 5.07; N, 11.13 0, 79.34; H, 5.07; N, 11.17

86.5 5 9 237.5-238 Gammon 01 c, 75.49; H, 4.22; N, 11.00 c, 75.29; H, 1.04; N 0.91

I 11 B3 III IV V VI \11 177 02.0 7 9 255-250 CWHHNQ:

- c, 85.08; H, 5.00; N, 0.02

0, 84.61; 11, 4.52; N, 10.57 c, 84.43; 11, 4.80; N, 10.58

130 01 05.0 5 8 182-1525 C H1eN Cl! 0,1540; 11, 4.22; N, 11.00 c, 75.32; 11, 4.42; N, 11.00

| c, 83.20; 11,5.05; N, 10.70 (I111 0,212.08; 11, 5.00; N, 10.83

152 O-CI{3 61). 5 9 ll-233 C351I1702N3 l 0,70. ,11,4.3s;N,10.74 Q 0,70 ,11,4.41;N,10.77

EXAMPLE 14 EXAMPLE 15 5.19 g. of benzitriazole derivative of formula 10.41 g. of 2-[4-methyl-phenyl-(1'.)]-5-[biphenylyl- (183) N (4)]-1,3,4-oxidiazole of formula Q CH (186) o '3 11 ll NN 3a (melting point: 119.5 to 120 C.), 4.53 g. of benzalaniline and 12.5 g. of potassium hydroxide powder containing about 10% of water are reacted in 150 ml. of dimethylformamide according to the instructions of Example 13 and are worked up. About 3.7 g., corresponding to 49.8% of theory, of the benztriazole compound of formula are obtained in the form of a light beige powder of melting point 194 to 194.5 C. Two recrystallisations from ethanol with the aid of activated charcoal yield colourless glistening platelets which melt at 196 to l96.5 C.

7.05 g. of 4-methoxybenzalaniline and 6.3 g. of potassium hydroxide powder containing about 10% of water are stirred into 200 ml. of dimethylformamide with exclusion of air, during which a bluish-tinged red colouration develops after a few minutes. The temperature is raised to 90 C. over the course of 45 minutes and the mixture stirred for a further 30 minutes at 90 to 95 C. and thereafter cooled to about 10 C. Now 100 ml. of water, 100 ml. of 10% strength hydrochloric acid and a further 250 ml. of water are added successively dropwise at 10 to 15 C. The precipitated reaction product is filtered 01f, Washed with water until neutral and freed of a =by-product by further washing with methanol. After drying about 9.8 g. corresponding to 68.3% of theory, of 2-[4-methoxy stilbenyl-(4')] 5 [biphenylyl-(4)]- 1,3,4'oxdiazole of formula Analysis.-C H N (297.34). Calculated (percent): C, 80.71; H, 5.09; N, 14.13. Found (percent) C, 80.74; H, 4.82; N, 14.21.

If instead of benzalaniline 6.43 g. of diphenyl-(4)- aldehyde-anil are used, then the compound of formula is obtained. Yield: 86.7% of theory. Pale greenish yellow glistening small needles from tetrac'hlorethylene. Melting point: 271 to 27l.5 C.

AnnIysis.-C H N (373.44). Calculated (percent): C, 83.62; H, 5.13; N, 11.25. Found (percent): C, 83.57; H, 5.22; N, 11.10.

listed in the following table may be prepared in a similar manner; in this, the reaction temperature was limited to 60 C. but 8 mols of potassium hydroxide per methyl group to be reacted were used. 

